Copper complex compounds of



Patented Feb. 16, 1954 UNITED STATES PATENT OFFICE COPPER COMPLEXCOMPOUNDS OF MONOAZO DYESTUFFS Albert Schmelzer,

Koln-Mulheim,

and 'Otto Bayer, Leverkusen-Bayerwerk, Germany, assignors toFarbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, acorporation of Germany No Drawing. Application May'l5, 1951, Serial No.226,528

Claims priority, application Germany May 19, 1950 6 Claims.

in which formula X stands for an alkyl radical or chlorine, the alkylradical having from 3 to 8 carbon atoms, and wherein the benzene nucleusR may be further substituted by radicals not causing water-solubility,in particular by chlorine. The alkyl radicals may be straight, branchedor cyclic.

According to the present invention these new copper-containing monoazodyestuffs are obtained by treating monoazo dyestuffs of the generalformula:

in which formula X and R means the same as stated above in analkaline-alcoholic solution with copper-yielding agents at elevatedtemperature. As a rule this reaction is carried out under refluxingconditions. In this reaction the chlorine atom standing in o-po-sitionto the azo bridge is exchanged for the hydroxyl group. The reaction withthe copper-yielding agents is car'- ried out in known manner in thepresence of such compounds as keep the copper-yielding agents dissolvedin alkaline medium. Compounds of this kind areas is known-e. g.polyhydroxy compounds or hydroxy-carboxylic acids.

The new copper-containing monoazo dyestufis are insoluble in water, butdissolve in all common organic solvents, such as ether, acetone,alcohol, esters, gasoline, benzene, toluene etc. with brown color. Inconsequence of this surprising solubility in a great variety ofsolvents, the new dyestuffs can be used for preparing spirit,nitrocellulose, cellulose ester, alkyd resin and transparent lacquers.Being, moreover, soluble in lacquers on the basis of polyisocyanates(cf. Farben, Lacke, Anstrichstofie 2, p. 123 [1948]), they can also beused therein. Furthermore, they can be used in the rubber printingprocess as well as for dyeing plastics being soluble in benzene,alcohol, esters or ketones, preparations for artificial silk, furniturestainings, waxes, fats, oils and gasoline. The dyeings, colorings andstainings obtained with the new copper-containing dyestuffs aredistinguished by a very good fastness to light.

The invention is illustrated by the following examples without beingrestricted thereto, the parts being by weight.

Example 1 54 parts of themonoazo dyestuff prepared by couplingdiazotized 3,4,6-trichloro-l-aminobenzene with4-tert.-buty1-l-hydroxybenzene, are stirred with 420 parts of alcoholand 30 parts of 40 per cent caustic soda solution, whereby most of thedye-stuif dissolves. A solution of 53 parts of crystalline coppersulfate in 225 parts of water, to which first parts of glycerine andthen 225 parts of about 40 per cent caustic soda solution are added, isrun into this mixture. Thereafter, further 500 parts of water are addedthereto. The reaction mixture is stirred for about 7 hours in the oilbath at an outside temperature of 140-150 C. with reflux. After coolingthe copper-containing dyestufi is sucked off, thoroughly washed withwater and dried at a temperature of 100 C. The dark-colored dyestufimelts at 206-207 C. It is the copper complex compound of the monoazodyestulf of the formula:

OH HO CIQN=N HaC-C-CH;

C lHa Analysis:

Found: C, 52.2%; H, 4.4%; N, 7.2%;

C1, 19.2%; Cu, 7.3%.

Example 2 Starting from 54 parts of the monoazo dyestufl prepared fromdiazotized 2,4,6-trichloro-1- aminobenzene and4-tert.-butyl-1-hydroxybenzene, and proceeding according to thedirections 217-220" (3., which is the copper complex of given in Example1, there is also obtained a brown, copper-containing dyestufl: fast tolight, which is the copper complex compound of the monoazo dyestuff ofthe formula:

on no CIQN=N I macs and melts at 213-214" 0., and is well suited e. g. l

as lacquer dyestufl.

Example 3 OH HO It is fast to light and can be used e. g. for dyeinglacquers.

Example 4 32.3 parts of the monoazo dyestuff prepared from diazotized2,5-dichloro-l-aminobenzene and i-tert-butyl-l-hydroxybenzene aredissolved in 140 parts of alcohol and about parts of 40pm cent causticsoda solution with stirring. Into this mixture a solution of 15 parts ofcrystalline copper sulfate in 60 parts of water, to which first 16 partsof tartaric acid and then parts of caustic soda solution are added, isrun, being followed by an addition of 175 parts of water. With stirringthe reaction mixture is refluxed for about 7 containing dyestufithus-obtained is sucked off and worked up as usual. The dark-coloreddyestufif melts at 170-175 C. and is thecopp'er complex compound of themonoazo dyestufi of the formula:

OH HO A Startingirom 34.3 parts oi the monoazo v"dye- L hours. Aftercooling the copper- 4 stufi prepared from diazotized 2,5-dichloro-1-aminobenzene and. 4-isooctyl-1-hydroxybenzene according to the procedureof Example 4, there is also obtained a brown, copper-containingdyestuff, which is the copper complex compound of a the monoazo dyestufiof the formula:

lsooctyl and melts at 153-156 C. It is well suited e. g. as lacquerdyestuff fast to light.

Example 6 30.2 parts of the monoazo dyestufi prepared from diazotized2,4-dichloro-l-aminobenzene and -chloro-l-hydroxybenzene are reacted tothe copper-containing dyestufl according to Example 4. The d'yestufithus obtained is a dark-colored powder with a melting point of 96 C.being the copper complex compound of the monoazo dyestufi of theformula:

It is well suited as a brown lacquer dyestuff fast to light.

Example '7 17 parts of the monoazo dyestufi prepared from diazotizedpentachloro-l-aminobenzene and 4- tert.-buty1-1-hydroxybenzene aresuspended with 140 parts of alcohol and about 10 parts of 40 per centcaustic soda solution. Into this mixture, :3. solution of 7.5 parts ofcrystalline copper sulfate in 30 parts of water, to which first 5 partsof glycerine and then 15 parts of caustic soda solution are added, isrun, being followed by the addition of parts of water. With stirring themixture is refluxed for about '7 hours. After cooling the diflicultlysoluble product is sucked off and washed with some alcohol. The alcoholof the filtrate is distilled off, and the separated dyestuff is suckedoff and thoroughly washed with water. It is the copper complex compoundof the monoazo dyestuff of the formula:

wherein X stands for one of the group consisting of alkyl radicalshaving from 3 to 8 carbon atoms and chlorine, and Y stands for one ofthe group consisting of hydrogen and chlorine, at least one of theradicals Y being chlorine, which coppercontaining dyestuffs are solublein common organic solvents with brown coloration.

2. As new products the copper complex compounds of monoazo dyestuffs ofthe general formula:

a r on OH HaC H aCHx wherein Y stands for one of the group consisting ofhydrogen and chlorine, at least one of the radicals Y being chlorine,which copper-containing dyestufis are soluble in common organic solventswith brown coloration.

3. As new product the copper complex compound of the monoazo dyestufi ofthe formula:

(RH OH being soluble in common organic solvents with brown colorationyielding dyeings fast to light.

4. As new product the copper complex compound of the monoazo dyestuff ofthe formula:

on on GPQAEN- mo cfiom being soluble in common organic solvents withbrown coloration yielding dyeings fast to light. 5. As new product thecopper complex compound of the monoazo dyestuff of the formula:

HaC JgCHs being soluble in common organic solvents with brown colorationyielding dyeings fast to light.

6. As new product the copper complex compound of the monoazo dyestufi ofthe formula:

H3C C JECH3 being soluble in common organic solvents with browncoloration yielding dyeings fast to light.

1. AS NEW PRODUCTS THE COPPER COMPLEX COMPOUNDS OF MONOAZO DYESTUFFS OF THE GENERAL FORMULA: 